DE1469664B2 - Use of condensation products containing sulfonic acid groups as dispersants for dyes that are poorly insoluble in water - Google Patents

Description

where A is the radical of an aromatic compound containing at least two condensed six-membered rings, R _{1 is} a benzene radical, R _{2 is} a hydrogen atom or an optionally further substituted benzoyl radical and m and η are each a whole positive number, or of water-soluble salts of sulfonic acids of this formula as a dispersant for in Water sparingly to insoluble dyes for high-temperature dyeing of synthetic polyamide, polyacrylonitrile or polyester fiber materials or cellulose acetate fiber materials, the amount of dispersant being 50 to 500 percent by weight, based on the dyes *. ·

2. Use of sulfonic acid group-containing condensation products according to claim !, characterized characterized in that they are made from naphthalene compounds, especially naphthalene sulfonic acids have been received.

3. Use of condensation products containing sulfonic acid groups according to claim 2, characterized in that characterized by being sulfonated by naphthalene under conditions prevalent Naphthalene-2-sulfonic acid and subsequent reaction with benzoin in the sulfonation mixture have been received.

4. Use of sulfonic acid group-containing condensation products according to claim 2, characterized characterized in that they have been obtained from benzyl halides, especially benzyl chloride are.

5. Use of condensation products containing sulfonic acid groups according to claim 2, characterized in that characterized by being sulfonated by naphthalene under conditions prevalent Naphthalene-2-sulfonic acid result, and subsequent reaction with benzyl chloride im Sulfonation mixture have been obtained.

The invention relates to the use of condensation products of the formula containing sulfonic acid groups

R ₁ "
-CH
R,

(—SO ₃ H) ,,,

in which A is the radical of an aromatic compound containing at least two condensed six-membered rings, R _{1 is} a benzene radical, R _{2 is} a hydrogen atom or an optionally further substituted benzoyl radical and m and η are each a whole positive number, or of water-soluble salts of the sulfonic acids of this formula as a dispersant for Dyes that are sparingly soluble to insoluble in water for high-temperature dyeing of synthetic polyamide, polyacrylonitrile or polyester fiber materials or cellulose acetate fiber materials, the amount of the dispersant being 50 to 500 percent by weight, based on the dyes. In the formula, η is preferably 1 or 2, and m is also usually a small number such as 1 or 2. The condensation products can be used in the form of the free acids or in the form of water-soluble salts, in particular sodium salts.

Such condensation products are expediently prepared by reacting reactive ones Aralkyl compounds with at least two fused six-membered rings containing aromatic sulfonic acids in the presence of sulfuric acid at elevated temperature.

Certain condensation products of the specified type can also be prepared by first allowing a reactive aralkyl compound to act on a compound free of sulfonic acid groups and containing at least two condensed six-membered rings and then sulfonating the condensation product obtained.
The aralkyl compounds used as starting materials in the production of the condensation products

__ are preferably those of the benzene series. There come for example aralkyl halides, especially aralkyl chlorides. Examples are benzyl bromide, Xylene chlorides and especially benzyl chloride mentioned. Furthermore, as reactive aralkyl compounds Benzoin and further substituted benzoins in the phenyl radicals should be mentioned.

Those also required as starting materials, containing at least two condensed six-membered rings aromatic compounds can, for example, be pure hydrocarbons or hydrocarbons be the only other substituents have sulfonic acid groups. There are different ring systems are contemplated provided that there are at least two fused aromatic six-membered rings in the molecule are present, what z. B. for acenaphthene, perylene, pyrene, phenanthrene and anthracene applies. Particularly Naphthalene is well suited.

Good dispersants for the present purpose can be prepared, for example, by im Molecular ratio 1: 1 to 2: 1 benzoin to naphthalene-2-sulfonic acid obtained by sulfonating naphthalene can act in the presence of condensing agents, as in the Swiss patents 130 420 and 133 377 is described.

A particularly effective dispersant for the present purpose can be obtained by sulfonation of naphthalene under conditions which give predominantly naphthalene-2-sulfonic acid, and then Prepare reaction with benzyl chloride in the sulfonation mixture (cf. British patent specification 240 318). As is known, mainly naphthalene-2-sulfonic acid is produced, when naphthalene is treated with concentrated sulfuric acid at about 170 to 180 "C. The benzyl chloride is then expediently at about 120 to 130 ° C the mixture after the sulfonation has ended added and the reaction at this or still

at a higher temperature, which can be seen from the cessation of the evolution of hydrogen chloride gas is.

As dyes that are sparingly soluble to insoluble in water, there are, for example, vat dyes, in particular but disperse dyes are considered. The dyes can also belong to different classes, the methine dyes, the anthraquinones, the nitro and the azo dyes are particularly mentioned.

According to the invention, the condensation products can have the composition specified at the outset Used wherever sparingly to insoluble dyes in fine aqueous dispersions must be transferred. For example, such dispersions can be produced with vat dyes, which then z. B. by the usual methods on textiles, preferably cellulose fibers, can be applied and vat. The condensation products are also suitable for production aqueous pigment dispersions.

Above all, however, they prove to be valuable when dyeing with disperse dyes. As fiber materials, that can be dyed with disperse dyes are cellulose acetate fibers, including triacetate fibers, Polyamide fibers, e.g. B. those from f-caprolactam, from adipic acid and hexamethylenediamine, from aminoundecanoic acid, polyacrylonitrile fibers and especially polyester fibers, in particular from polyterephthalic acid glycol ester to mention.

The condensation products can, for example, be added to the dye baths and printing pastes, which serve to dye the fiber materials mentioned in the usual way with disperse dyes or to print. So you can, expediently in continuous operation, an aqueous preparation, a disperse dye and a condensation product to be used according to the invention contain, on fiber material, e.g. B. Apply fabric made of polyester fibers and the material loaded in this way after drying for a short time at a high temperature, e.g. B. about 200 ° C, expose.

The condensation products of the specified composition prove to be particularly advantageous in the so-called high-temperature dyeing of polyester fibers with disperse dyes. This dyeing method is carried out in closed vessels under pressure and at temperatures of over 100 ^° C., for example between HO and 140 ^° C. So that the pressure vessels can be kept as small as possible, one generally works with a relatively short liquor. As a rule, the material to be dyed rests, e.g. B. can be present as loose material, strand, piece or in the form of bobbins in the dyeing machine, and the liquor circulates through the material to be dyed. It is important that a fine dispersion of the dye is not only present initially, but that the degree of dispersion is maintained throughout the entire dyeing process. Certain disperse dyes tend to turn into a less fine form under high temperature dyeing conditions. The consequence of this is that the dye no longer absorbs onto the fiber and settles on the surface of the material to be dyed. Such dye deposits can be avoided particularly well by the condensation products to be used according to the invention.

For example, 50 is used to disperse the dyes, which are sparingly soluble to insoluble in water up to 500% condensation product, based on the "amount of dye. You can use the dye and the Process the condensation product into a permanent preparation that can be used in anhydrous or water-containing Form, e.g. as dough. But you can also use dyes mixed with other dispersing agents for dyeing by one of these preparations, the condensation products to be used according to the invention z. B. in manufacture the dye liquor added. In the former case, new dye preparations result are marked that they

a) Insoluble to insoluble in water, for dyeing textile fibers by the dispersion process suitable dyes and

b) Condensation products containing sulfonic acid groups from reactive aralkyl compounds and aromatic compounds containing at least two fused six-membered rings

in fine distribution, preferably in an aqueous dispersion.

In the following examples as in the preceding description, unless otherwise it is noted that the parts are parts by weight and the percentages are percentages by weight.

example

1 part of an aqueous paste of the dye of the formula is ground

CH ₂ -OC

Il ο

N = N-C

OH

C-N

C = N

CH ₃

with 1.5 parts of U'-dinaphthylmethane ^^ '- disuIfonsaurem Sodium in a ball mill to a fine dough with a 10% dye content.

60 parts of this dye preparation and 2 parts of 1-methyl-2-heptadecylbenzimidazole-sulfonic acid sodium are stirred with 2000 parts of water. 7 parts

Condensation product obtained from naphthalene-2-sulfonic acid and benzyl chloride are added. A dye bath of 7000 parts is prepared from it by diluting it with water. The pH is adjusted to 5 to 6 with acetic acid.

In this bath is at 50 ° C with 300 parts of a purified 'polyester fiber woven fabric a, the temperature is raised within half an hour at 120 to 130 ⁰ C and stained for 1 hour in a closed circulatory system at this temperature. Then it is rinsed well. A yellow dyeing with very good rub fastness is obtained.

If you work otherwise in the same way, but without the addition of the condensation product, you get an uneven and dye which is not rubbed out, and much of the dye separates out in flakes. The condensation product prevents agglomeration of the dye, so that the fiber material is free from dye deposits is.

The condensation product mentioned above can be prepared as follows:

120 parts of 95% pure sulfuric acid are introduced ^{into 100 parts of naphthalene at 160 ° C., and the mixture is kept at 170 to 180 °} C. for 7 to 8 hours, ie until a sample is clearly soluble in water. After cooling to 120 ° C., 100 parts of benzyl chloride are slowly added. The temperature is initially, when no more hydrogen chloride gas escapes, raised to 130 ⁰ C and 170 ⁰ C and held for 15 minutes at 170 ° C. After cooling to 130 ° C., the reaction mixture is poured into 500 parts of an ice-water mixture, neutralized with calcium hydroxide, for which about 80 parts are required, filtered off and washed with a little water. Sodium carbonate is added to the filtrate until no further precipitation occurs (about 130 parts). It is then filtered and the filtrate is evaporated to dryness. About 210 parts of water-soluble condensation product are obtained.

Example2

If you use the method described in Example 1 300 parts of polyester fibers with 45 parts a 10% dough of the dye of the formula

C = CH

CH,

CH, -CH, -O-C

CH ₂ -CH ₂ -OC

colors, the addition of the condensation product described in Example 1 also gives a level and rubbing-fast dyeing, while without this addition some of the dye is removed from the dye bath flocculates and is deposited in this form on the surface of the fiber.

The condensation product can also be used in place of the l, l'-dinaphthylmethane-2,2'-disulfonic acid sodium can be used in the aqueous dispersion of the dye in the ball mill. You get in this way a dough which dyes polyester fiber fabric perfectly, especially when in Presence of a small amount of a sulfonated one which is substituted in the 2-position by a longer alkyl radical Benzimidazole is worked.

B e i s ρ i e 1 3

The procedure is as in Example 1, but instead of the condensation product of naphthalene-2-sulfonic acid and benzyl chloride the same amount of condensation product of naphthalene-2-sulfonic acid and Benzoin to and colors in the specified way. A dyeing with very good rub fastness is obtained.

The above-mentioned condensation product is prepared as follows:
A mixture of 65 parts of naphthalene and 130 parts of 95% pure sulfuric acid is ^{kept at 160 °} C. for about 7 hours. After allowing to cool, 300 parts of sulfuric acid are slowly added and 106 parts of benzoin are introduced over the course of about 15 minutes with thorough stirring at 40 to 50 ° C. The temperature is slowly increased to 80 ^° C. and kept at 80 to 90 ^° C. for 8 hours. The reaction mixture is poured onto 3000 parts of water. The product is dissolved at 80 ⁰ C, filtered off from insoluble residues, precipitated with 200 parts of sodium chloride, suction filtered and dried. For use, the product obtained in this way is expediently dissolved in hot water, neutralized and then added to the dyebath.

B e i s ρ i e 1 4

When dyeing according to Example 2, the condensation product of naphthalene-2-sulfonic acid is used and benzyl chloride the same amount of condensation product of naphthalene-2-sulfonic acid and Benzoin too. A dyeing with very good rub fastness is obtained.

Example5

The procedure is as in Example 1, but instead of the condensation product of naphthalene-2-sulfonic acid and benzyl chloride the same amount of condensation product of phenanthrene sulfonic acid and Benzyl chloride and colors in the manner indicated. A dyeing with very good rub fastness is obtained.

The condensation product mentioned above is produced as follows:

A mixture of 140 parts of phenanthrene, and 1,000 parts of 90% sulfuric acid is slowly heated to 110 ° C and held for about 2 hours at 110 to 120 ⁰ C. 100 parts of benzyl chloride are allowed to flow in over the course of one hour. The temperature is slowly increased to 170 ° C and held at 170 ° C for 15 minutes. After allowing to cool, the reaction mixture is poured onto 600 parts of an ice-water mixture, neutralized with calcium hydroxide, which requires about 620 parts, filtered off and the residue is washed with a little hot water. 1100 parts of 10% sodium carbonate solution are added to the filtrate. It is then filtered and the filtrate is evaporated to dryness. About 275 parts of water-soluble condensation product are obtained.

At game 6

The procedure is as in Example 1, but instead of the condensation product of naphthalenesulfonic acid and benzyl chloride, the same amount of the condensation product of 1-methylnaphthalene-sulfonic acid and benzyl chloride and colors in the specified

Way. A dyeing with good rub fastness is obtained.

The abovementioned condensation product is prepared from 110 parts of 1-methylnaphthalene according to in example 1 specified procedure.

Example7

If you use the method described in Example 1 500 parts polyester fibers with ^ parts a 10% dough of the dye of the formula

Example 8

If, according to the working method described in Example 1, 500 parts of polyester fibers with 100 parts a 10% dough of the dye of the formula

NH

SO ₂ - HN

IO NO,

O NH,

O-CH, -CH, -OH

O OH

colors are obtained with the addition of that described in Example 1 Condensation product a rub-fast pink color.

colors, the addition of the condensation product described in Example 1 gives a non-rubbing product yellow coloring.

Example 9

The dyebath described in Example 1 35 parts by volume of a mixture of 78 parts of o-dichlorobenzene, 20 parts of partially neutralized butylnaphthalenesulfonic acid and 2 parts of conc. Ammonia added. In this bath is at 3O ⁰ C with 300 parts of a purified polyester fabric A, the temperature is raised within half an hour at 100 ° C and stained for 1 hour in a closed circulatory system at this temperature. Then it is rinsed well. A yellow dyeing with very good rub fastness is obtained.

example

A mixture of 25 parts of dye 1: 2 chromium complex of the monoazo dye of the formula

COOH

N = N-C

50 parts of thiodiglycol, 50 parts of thiourea, 235 parts of water and 30 parts of condensation product from naphthalene-2-sulfonic acid and benzyl chloride is boiled and stirred into 550 parts of crystal rubber thickening 1: 2, whereupon 30 parts of 33% ammonium tartrate solution are added.

A polyamide fabric is printed with the printing paste thus obtained. After printing, this will be

C-N

Fabric dried and then steamed for 20 minutes without excess pressure. You get a uniform yellow print that penetrated well to the back of the fabric. Do you work otherwise same, but in the absence of the condensation product, a poorly dispersed, coarser paste and an irregular, speckled, superficial print.

Example 50 parts of 1: 2 chromium complex of the monoazo dye of the formula

OH COOH

= N-C

C-N

C = N

are with the addition of 50 parts of the condensation product of naphthalene-2-sulfonic acid and benzyl chloride (produced according to Example 1) in 200 parts

CH ₃

80% acetic acid stirred evenly. The mixture is evaporated to dryness in a vacuum until the acetic acid odor disappears

409 543/317

The following filter test is carried out with a sample of this: 2 g of the dye preparation are added to 200 ml sprinkled with cold water. The mixture is stirred at high speed for 3 minutes. Well will in a vacuum through a filter paper with a diameter of 7 cm (No. 1450 CV, Carl Schleicher & Schüll) filtered. As soon as there is no more liquid on the filter, it is rinsed with 50 ml of water.

No residue remains on the filter. If you work the same way, but with dinaphthyl- (l, l ') - methane-2, 2'-disulfonic acid sodium, a lot of residue is obtained on the filter. With this dye preparation Polyamide fibers can be dyed by those dyeing methods that are suitable for water-soluble fibers 1: 2 chromium complexes are suitable.

Claims (1)

Patent claims: 1. Use of condensation products of the formula containing sulfonic acid groups R, -CH ■ 2 Jn (-SO ₃ H) ,,,